US3824228A - Oligopeptide derivatives and process for the preparation thereof using glycidyl esters of carboxylic acids to react with protein-diamine aminolyzates - Google Patents

Oligopeptide derivatives and process for the preparation thereof using glycidyl esters of carboxylic acids to react with protein-diamine aminolyzates Download PDF

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Publication number
US3824228A
US3824228A US00294187A US29418772A US3824228A US 3824228 A US3824228 A US 3824228A US 00294187 A US00294187 A US 00294187A US 29418772 A US29418772 A US 29418772A US 3824228 A US3824228 A US 3824228A
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Prior art keywords
protein
carbon atoms
acid
aminolyzates
preparation
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US00294187A
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English (en)
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H Eckert
P Nikolaus
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Classifications

    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/64—Proteins; Peptides; Derivatives or degradation products thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/64—Proteins; Peptides; Derivatives or degradation products thereof
    • A61K8/65—Collagen; Gelatin; Keratin; Derivatives or degradation products thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07K—PEPTIDES
    • C07K1/00—General methods for the preparation of peptides, i.e. processes for the organic chemical preparation of peptides or proteins of any length
    • C07K1/12—General methods for the preparation of peptides, i.e. processes for the organic chemical preparation of peptides or proteins of any length by hydrolysis, i.e. solvolysis in general
    • C07K1/126—Aminolysis

Definitions

  • the invention relates to. a process for the preparation .Iof .novel oligopeptide derivatives which can be used in hair conditioning and cosmetic preparations.
  • oligopeptide derivatives are known as useful textile'softeners, which are preparable .jby two-stage reaction of proteinaminolyzates with longchain epoxides and subsequent acylation with fatty acids or fatty acid esters.
  • oligopeptide derivatives for .use in :hair cosmeticfcompositions comprising reacting QA) a protein aminolyzate. consisting essentially of the @reri'ction productof a protein with an amine selected from .the group consisting of diamine with 2 to carbon -atomsand polyamine with 2 to 10 carbon atoms, with ,carbon atoms; and recovering isaid oligopeptide derivatiyes; and the oligopeptide derivatives produced thereby.
  • a 3 DESCRIPTION OF THE INVENTION imend-compositions comprisingreacting (A) a protein an aliphatic hydrocarbon. having 9 to 23 aminolyzate consisting essentially of the reaction product of a protein with an amine selected from the group consisting of diamine with 2 to 10 carbon atoms and polyamine with 2 tom carbon atoms, with (B) a glycidyl ester of a carboxylic acid of the formula 0 o R %l o cH.-ot- CH.
  • R is an aliphatic hydrocarbon having 9 to 23 carbon atoms
  • the protein-aminolyzates used as starting materials in the process according to the invention may be derived from any vegetable or animal proteins, for example glue, gelatin, albumin, collagen, keratin, casein, protein derived from feathers, hair protein, cottonseed protein or soya protein.
  • glue for the aminolysis of such proteins, diamines and/or polyamines with 2 to 10 carbon atoms are used. These amines are preferably those aliphatic amines having the formula:
  • the aminolysis of the proteins with the above-mentioned diamines and/or polyamines may be efiected in known way by heating the proteins with at least an equal amount by weight of diamine and/or polyamine under reduced pressure at temperatures between and 200 C. until an aliquot part of the reaction mixture is soluble in dilute acid.
  • a preferred embodiment for carrying out the aminolysis comprises adding an amount by weight of water, equal to or greater than the amount by weight of protein, to an amount by weight of diamine or polyamine which is equal to the weight of protein, heating the amine water mixture at C. to C. in a protective gas and then adding the protein. The temperature was then, also in presence of protective gas, raised to C. As soon as the reaction product was soluble in acid, water and excess amine which might be present were removed under reduced pressure.
  • the molecular weights of the aminolyzates from proteins and the above-described diamines and/or polyamines generally lie in the range of 300 to 1000.
  • Preferred starting substances for. the process according to the invention are aminolyzates with a molecular weight lying in the range from 350 to 700.
  • aminolyzates are then reacted with glycidyl esters of carboxylic acids of the general formula:
  • R signifies an aliphatic hydrocarbon containing 9 to 23 carbon atoms.
  • the aliphatic hydrocarbon R may be a straight or branched chain and be saturated or unsaturated.
  • Ris'a straight chained member selected from ,the group consisting of alkyl of 9 to 23 'carbon atoms, alkenyl of 9 to 23 carbon atoms, alkadienyl of 9 to 23 carbon atoms, hydroyalkyl of 9 to 23 carbon atoms, hydroxalkenyl of 9' to 23 carbon atoms, alkatr'ienyl of 9 to 23 carbon atoms, and the mixtures thereof.
  • suitable glycidyl esters of naturally occurring fatty acids are, for example alkanoic acids of 10 to 24 carbon atoms such as capric acid, lauric acid, rnyristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, and lignoceric acid, alkenoic acids of to 24 carbon atoms such as oleic acid and erucic acid, hydroxyalkanoic acids of 10' to 24 carbon atoms such as hydroxy-stearic acid, hydroxyalkenoic acids of 10 to 24 carbon atoms such as ricinoleic acid, alkadienoic acids of 10 to 24 carbon atoms such as linoleic acid, alkatrienoic acids of 10 to 24 carbon atoms such as linolenic acid, and the mixtures thereof, such as for example glycidyl esters of fatty acid fractions.
  • Other suitable glycidyl ester reactants include the glycidyl ester
  • the relative proportions of the protein aminolyzate and the glycidyl ester of a carboxylic acid may vary within specified limits, depending on the type and molecular weight of the aminolyzate used. However, the range of 1 to 3 mol of glycidyl esters per mol of aminolyzate are preferable, since the products produced are more easily dispersible in water or water/alcohol mixtures.
  • the temperatures to be used lie in the range of 70 C. to 150 C. Basically the reaction may be carried out without use of a solvent. Since, however, the reaction is strongly exothermic and local overheating influences the color quality of the products, the addition of a solvent in which the aminolyzates are soluble or at least dispersible is preferable. Suitable solvents are, for example, lower alcohols and/ or water.
  • the reaction may be carried out by adding the glycidyl ester portionwise to the aminolyzate heated to the desired reaction temperature, to which a solvent is optionally added, and thoroughly mixing the reaction material. After the termination of the glycidyl ester addition, heating and thorough mixing of the reaction mixture-possibly after increasing the temperature-4s continued until epoxide oxygen is no longer detectable.
  • the separation of the solvent which may be present, may be effected by distillation before or during the period subsequent to the reaction.
  • the products are obtained in the form of a highly viscous mass, which on cooling, solidifies to solids of yellowish to brown color, depending on the reaction conditions.
  • the products can be purified by recrystallization from acetone or similar solvents.
  • the oligopeptide derivatives preparable according to the invention are probably 2,3 dihydroxypropylcarboxylic acid amides.
  • residues of aminoalcohol esters may also be present in the products.
  • the products preparable according to the invention are readily dispersible in water and water/alcohol mixtures. They are readily adsorbed on hair and show superior results with regard to general hair cosmetic activity than the protein hydrolyzates previously used for this purpose, and on the market such as may be obtained, for example,
  • Protein-aminolyzate A A mixture of 1 kg. of diethylenetriamine and 2 kg. of water was heated in a round-bottomed flask to 90 C. 1 kg. of gelatin was added with stirring during a period of half an hour, and then the reaction temperature was raised to 110 C. Water and excess amine were distilled off in vacuo. The protein-aminolyzate product wasobtained in the form of a paste after the cooling thereof, and it had an average molecular weight of 385.
  • Protein-aminolyzate B Aminolysis product fromcasein'and diethylenetriamine, average molecular weight 1 V 550.
  • EXAMPLEI 116 g. (about 0.3 mol) of protein-aminolyzate A were heated with 60 ml. ofwater to C. to C., 162 g. (0.6 mol) of glycidyl laurate were added dropwise while vigorously stirring the mixture; and then the mixture was stirred at 80 C. to 90 C. fora further 3, hours. Afterwards water was distilled off in vacuo at C.; and the reaction mixture was maintained for a further 3 hours at C. The resulting yellowish melt solidified on cooling to a yellow solid, which had a total nitrogen content of 9.49% and an amino nitrogen content of 1.77% The OH value of the product was 230.
  • EXAMPLE 2 116 g. of protein-aminolyzate A (about 0.3 mol) were reacted with 212 g. (0.6 mol) of glycidyl oleate by the method according to Example 1. The resulting yellow solid had a total nitrogen content of 6.45%, an amino nitrogen content of 2.03% and an OH value of 220.
  • EXAMPLE 4 The products produced in Examples 1 to 3 were re spectively incorporated in quantities of 1% by weight based upon the weight of the total composition, into hair treatment mixtures of known composition. Human models with hair of damaged structure were chosen for the test series. The hair was washed, brushed and parted in the center. Then the preparation of the present invention was applied to one half of the head and a comparative prior art preparation was applied to the other half of the head. After a treatment time of 15 minutes, the hair was rinsed out with warm water, brushed and the body of thehair and the wet combability of the hair were judged by 6 skilled persons.
  • Analogous results could be obtained with reaction products from protein-aminolyzate B and glycidyl esters of myristic acid, palmitic acid, behenic acid or erucic acid as well as with reaction products from protein-aminolyjrate C with glycidyl esters of lauric acid,oleic acid or inyristic acid.
  • a process for the preparation of oligopeptide derivatives for use in hair cosmetic compositions comprising reacting at a temperature in the range of 70 C. to 150 C.
  • R is selected from the group consisting of alkyl of 9 to 23 carbon atoms, alkenyl of 9 to 23 carbon atoms, alkadienyl of 9m 23 carbon atoms, alkatrienyl of 9 to 23 carbon atoms, hydroxyalkyl of 9 to 23 carbon atoms, hydroxy alkenyl of 9 to 23 carbon atoms, and the mixtures thereof.
  • the natural protein is selected fromuthe group consisting of glue, gelatin, albumin, collagen, keratin, caesin, protein derived, from feathers, hair protein, cottonseed protein and soya protein.
  • the aliphatic amine is selected from the group consisting of ethylenediamine, 1,4 diaminobutane, diethylenetriamine, 1,6 diaininohexane, triethylenetetramine, and tetraethylenepentamine.

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  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Animal Behavior & Ethology (AREA)
  • Birds (AREA)
  • Epidemiology (AREA)
  • Organic Chemistry (AREA)
  • Biophysics (AREA)
  • Biochemistry (AREA)
  • Genetics & Genomics (AREA)
  • Medicinal Chemistry (AREA)
  • Molecular Biology (AREA)
  • Proteomics, Peptides & Aminoacids (AREA)
  • Analytical Chemistry (AREA)
  • Cosmetics (AREA)
  • Peptides Or Proteins (AREA)
US00294187A 1971-10-18 1972-10-02 Oligopeptide derivatives and process for the preparation thereof using glycidyl esters of carboxylic acids to react with protein-diamine aminolyzates Expired - Lifetime US3824228A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE2151739A DE2151739C3 (de) 1971-10-18 1971-10-18 Verfahren zur Herstellung neuer als haarkosmetische Wirkstoffe brauchbarer Oligopeptidderivate

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US3824228A true US3824228A (en) 1974-07-16

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US (1) US3824228A (OSRAM)
AT (1) AT330804B (OSRAM)
CH (1) CH580571A5 (OSRAM)
DE (1) DE2151739C3 (OSRAM)
FR (1) FR2156780B1 (OSRAM)
GB (1) GB1364991A (OSRAM)
IT (1) IT1001508B (OSRAM)
NL (1) NL7212956A (OSRAM)
SE (1) SE389120B (OSRAM)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4076800A (en) * 1975-01-13 1978-02-28 The Procter & Gamble Company Protein-containing detergent compositions for protecting keratinous materials
US4115548A (en) * 1974-01-18 1978-09-19 The Procter & Gamble Company Detergent compositions comprising modified proteins
US4338214A (en) * 1979-11-08 1982-07-06 Henkel Kommanditgesellschaft Auf Aktien (Henkel Kgaa) Mild-to-the-skin anionic tensides of basic protein aminolysates preparations containing them, and their use
US4369037A (en) * 1980-11-19 1983-01-18 Kao Soap Co., Ltd. Hair treatment cosmetics containing cationic keratin derivatives
US4705682A (en) * 1985-05-13 1987-11-10 Henkel Kommanditgesellschaft Auf Aktien Oligopeptide derivatives, their production and their use as surfactants gentle to the skin
WO2009010314A1 (de) * 2007-07-17 2009-01-22 Henkel Ag & Co. Kgaa Haarbehandlungsmittel mit oligopeptiden

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA1166576A (en) * 1980-08-19 1984-05-01 Lorna C. Staples Whey protein containing cosmetic formulations
EP0109074A1 (en) * 1982-11-16 1984-05-23 Inolex Chemical Company Quarternary ammonium derivatives of amino acid units
ES2241430B1 (es) * 2003-04-04 2006-12-01 Actherm Inc. Termometro electronico dotado de visualizacion por pantalla de cristal liquido ajustable en orientacion.

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3138581A (en) * 1959-10-12 1964-06-23 Swift & Co Surface active acylated amidated peptides and polypeptides
FR1520356A (fr) * 1961-12-06 1968-04-12 Tech B E T Bureau Et Procédé de traitement de protéines ainsi que de leurs produits d'hydrolyse et produits ainsi obtenus
DE1959651C3 (de) * 1969-11-28 1973-11-15 Henkel & Cie Gmbh, 4000 Duesseldorf Verfahren zur Herstellung lag kettiger Alkylol und Acylgruppen ent haltender Oligopeptiddenvate

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Chem. Abstracts, Vol. 75, 1971, 99227N, Eckert et al., effective date Mar. 6, 1971 *

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4115548A (en) * 1974-01-18 1978-09-19 The Procter & Gamble Company Detergent compositions comprising modified proteins
US4076800A (en) * 1975-01-13 1978-02-28 The Procter & Gamble Company Protein-containing detergent compositions for protecting keratinous materials
US4087518A (en) * 1975-01-13 1978-05-02 The Procter & Gamble Company Foaming and conditioning protein-containing detergent compositions
US4338214A (en) * 1979-11-08 1982-07-06 Henkel Kommanditgesellschaft Auf Aktien (Henkel Kgaa) Mild-to-the-skin anionic tensides of basic protein aminolysates preparations containing them, and their use
US4369037A (en) * 1980-11-19 1983-01-18 Kao Soap Co., Ltd. Hair treatment cosmetics containing cationic keratin derivatives
US4705682A (en) * 1985-05-13 1987-11-10 Henkel Kommanditgesellschaft Auf Aktien Oligopeptide derivatives, their production and their use as surfactants gentle to the skin
WO2009010314A1 (de) * 2007-07-17 2009-01-22 Henkel Ag & Co. Kgaa Haarbehandlungsmittel mit oligopeptiden

Also Published As

Publication number Publication date
FR2156780A1 (OSRAM) 1973-06-01
SE389120B (sv) 1976-10-25
IT1001508B (it) 1976-04-30
CH580571A5 (OSRAM) 1976-10-15
DE2151739A1 (de) 1973-04-26
AT330804B (de) 1976-07-26
DE2151739B2 (de) 1975-03-20
ATA889772A (de) 1975-10-15
DE2151739C3 (de) 1975-10-30
FR2156780B1 (OSRAM) 1978-05-26
NL7212956A (OSRAM) 1973-04-24
GB1364991A (en) 1974-08-29

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